Substituted 4,4-bis(2-(1,3,4-oxadiazolyl)) stilbenes



United States Patent 3,511,834 SUBSTITUTED 4,4-BIS(2-[1,3,4-OXADIAZOLYL]) STILBENES Adolf Emil Siegrist, Basel, Erwin Maeder, Aesch, Basel- Land, Peter Liechti, Binningen, and Leonardo Guglielmetti, Birsfelden, Switzerland, assignors to Ciba Limited, Basel, Switzerland, a company of Switzerland No Drawing. Continuation-impart of application Ser. No. 463,323, June 11, 1965. This application Sept. 5, 1967, Ser. No. 665,298

Claims priority, applicatiog6S/witzerland, June 15, 1964,

1, 64 Int. Cl. C07d 85/54 US. Cl. 260-240 11 Claims ABSTRACT OF THE DISCLOSURE New 4,4'-disubstituted stilbenes are provided which may be represented by the general formula CROSS-REFERENCES TO RELATED APPLICATIONS This is a continuation-in-part of application Ser. No.

463,323, filed June 11, 1965, now abandoned.

SUMMARY OF THE INVENTION The present invention provides new 4,4'-disubstituted stilbenes which may be represented by the general formula where A and A are identical or difierent and each repre- 'ice able, new 4,4-disubstituted stilbenes of the general formula wherein A and A represents a member selected from the group consisting of the phenyl, naphthyl, styryl, stilbenyl, pyridyl, thienyl, furoyl, benzoxazolyl thienyl and benzoxazolyl phenyl residue which itself may contain one to two substituents Q, in which Q stands for a member selected from the group consisting of hydrogen, halogen, alkyl containing 1 to 18, preferably 1 to 12 carbon atoms, alkoxy containing 1 to 8 carbon atoms, phenyl, carboxyl, carboxylic acid alkyl ester containing 1-18, preferably 1 to 12 carbon atoms in the alkyl portion, carboxylic acid phenylalkylester with 1-4 carbon atoms in the alkyl, carboxylic acid amide, nitrile, carboxylic acid monoalkyl amide and dialkylamide with 1 to 12 carbon atoms in the alkyl portion, carboxylic acid morpholide, carboxylic acid anilide, carboxylic acid phenylalkyl amide with l-4 carbon atoms in the alkyl, sulfonic acid, sulfonic acid alkyl ester containing l-18, preferably 1 to 12 carbon atoms, sulfonic acid benzylester, sulfonic acid phenyl ester, sulfonic acid amide, sulfonic acid alkyl amide containing 1 to 18, preferably 1 to 12 carbon atoms, sulfonic acid benzylamide and sulfonic acid anilide.

Preferred compounds of the Formula 1 are those which are of a symmetrical structure and correspond to the formula where A represents a member selected from the group consisting of a phenyl, naphthyl and styryl residue which itself may contain one to two substituents Q, in which Q stands for a member selected from the group consisting of hydrogen, halogen, alkyl containing 1-8 carbon atoms, alkoxy containing 1-8 carbon atoms, phenyl, carboXyl, lower alkyl carboxylic acid ester, carboxylic acid amide, nitrile, sulfonic acid, lower alkyl sulfonic acid ester and sulfonic acid amide.

Compounds of specific interest are those of Formula 2 sents an aryl, an aralkenyl radical forming a system of where Q represents a member selected from the group conjugated double bonds with the aryl radical and the diazole nucleus or a heterocyclic radical of aromatic nature; R represents hydrogen, halogen, alkyl, halogen alkyl, cyano, cyanoalkyl, the carboxyl group, the carboxylic acid ester group and the carboxylic acid amide group.

consisting of hydrogen, halogen, alkyl containing 1-8 carbon atoms, alkoxy containing 1 to 8 carbon atoms, phenyl, car-boxyl, lower alkyl carboxylic acid ester, carboxylic acid amide, sulfonic acid, lower alkyl sulfonic acid ester and sulfonic acid amide, as well as those of the formula 4 Where Q represents a member selected from the group with a monocarboxylic acid hydrazide of the formula :onsisting of hydrogen, halogen, alkyl containing 1-8 car- :on atoms, alkoxy containing 1 to 8 carbon atoms, phenyl, (10) :arboxyl, carboxylic acid alkyl ester with 1 to 8 carbon ttoms in the alkyl, carboxylic acid amide, sulfonic acid, rulfonic acid alkyl ester with 1 to 8 carbon atoms and HNNH2 :ulfonic acid amide.

Special mention among the compounds of Formula 2 As examples of carboxylic acids of the formula ieserve those which correspond to the formula 1 A-COOH Whose halides or hydrazides are suitable as where Q, represents an alkyl group containing 1 to 4 car- 011 atoms. starting materials for the manufacture of acylhydrazides Another specific group of compounds according to Forof the Formula 6 there may be mentioned:

nula 2 corresponds to the formula where Q represents the sulfonic acid group, Water soluble Benzenecarboxylic acids of the formulae salt of the sulfonic acid, sulfonic acid alkyl amide con- :aining 1 to 12 carbon atoms, sulfonic acid alkyl ester (11) COOH :ontaining l to 12 car-hon atoms, and the sulfonic acid phenyl ester which may be substituted by lower alkyl.

Preferred compounds according to Formula 4 are those which correspond to the formula where X stands for hydrogen, alkali metal, earth alkali (12) metal, ammonium or an amine salt ion. H

The new stilbene derivatives of the Formula 1 can be Q1 prepared by methods as such known. Symmetrical com- 1 pounds of the Formula 1, are Obt When y y where Q, has the same meaning as in the Formula 2, such zines of the formula as 2-, 3- or 4-methylbenzenecarboxylic acid, 2-, 3- or 4- chlorobenzenecarboxylic acid, 4-tertiary butylbenzene- (6) carboxylic acid, 4-n-octylbenzenecarboxylic acid, 2-, 3- or A-C (|3(JH=CHC CA 4-methoxybenzenecarboxylic acid, 2-, 3- or 4-ethoxybenand l, l i 5O zenecarboxylic acid, 4-octylhydroxybenzenecarboxylic acid, 2-, 3- or 4-sulfobenzenecarboxylic acid, 2-, 3- or 4- where the two As are identical radicals of the indicated carboxybenzenecarboxylic acid; furthermore naphthalenekindare treated with dehydrating agents, especially with aor -fi-carboxylic acid, cinnamic acid, 2-chlorocinnamic thionyl hloride. acid, 2- or 3-methylcinnamic acid, pyridine-2-, -3- or -4- The symmetrical acylhydrazines of the Formula 6 carboxylic acid, furan-Z-carboxylic acid and thiophenethemselves are obtained by reacting in the molecular ratio carboxylic acids such as thiophene-Z-carboxylic acid, 3- of 1:2 stilbene-4,4'-dicarboxylic acid dihydrazide of the or 5-methylthiophene-Z-carboxylic acid, 3,5-dimethylf l thiophene-Z-carboxylic acid.

The reactions required to manufacture the symmetrical v dioxdiazolyl-stilbenes of the Formula 1 and the starting o CH=CH-G materials of the Formula 6 can be performed in the usual, ENPNHZ known manner. 'Inter alia, the acid chlorides are reacted with the acid hydrazides advantageously in the presence with a monocarboxylic acid chloride of the formula f an acid acceptor gin a pyr n b e S ch as a pico- (8) v 0 line or in pyridine.

A dehydrating agent particularly suitable for the conversion of acylhydrazines of the Formula 6 into symmet- Cl rical di-oxdiazolyl-stil'benes of the Formula 1 is thionyls I chloride, among other reasons because the ring closure or st1lbene-4,4 -dicarboxylic acid dichloride of the formay be performed in an excess f this dehydrating agent, 1 1 8 which at the same time acts also as solvent, whereupon (9) v 0 the unconsumed thionylchloride can be removed with O jj} l It has proved partlcularly advantageous to perform the C reaction giving rise to the corresponding acylhydrazines also obtained when mixtures of sulfur (in a stoichiometric excess) and methylphenyl oxdiazoles of the formula are heated to temperatures above 200 C. This route can be represented by the following formulae:

H NN HSH tion of thionylchloride at the boiling temperature of the reaction mixture (at a temperature from 120 to 220 C.), proceeds very rapidly and smoothly, that is to say that the manufacture of compounds of the Formula 1 or 2 starting from the hydrazines can unexpectedly be carried out as a one-stage process.

Asymmetrical stilbene derivatives of the Formula 1 are obtained when diacylhydrazines of the formula O OCH;

whereupon the resulting acylhydrazine of the formula HN-NH OCH:

is treatedif necessary after first having been isolatedwith a dehydrating agent, especially thionylchloride. In the so formed oxdiazolylstilbene derivative of the formula ll ll NN the carboxylic acid methyl ester group bound with the stilbene radical is converted into a carboxylic acid hydrazide group and the corresponding monoacylhydrazmes are condensed with monocarboxylic acid chlorides of the formula AiC\ OCH;

to form the diacylhydrazines of the Formula 13. For this purpose there may be used as monocarboxylic acid chlorides of the Formula 17 those of the monocarboxylic acids mentioned above.

New 4,4'-disubstituted stilbenes of the Formula 1a are According to another process for the manufacture of 4,4'-disubstituted stilbenesof the Formula la dihydrostilbene compounds of the formula O NN where A and A have the above meaningsare treated with a dehydrogenating agent e.g. with sulfur, chlorine or with palladium and air.

The oxdiazole derivatives of the present invention can also be prepared by the action of imidoethers upon the corresponding carboxylic acid hydrazides at elevated temperatures and in the presence of a solvent.

The new optical brighteners of the composition defined above display in the dissolved and finely dispersed state a more or less pronounced fluorescence. They may be used for optically brightening a very wide variety of high-molecular or low-molecular organic materials or materials containing organic substances.

As examples of such materials the following groups of organic materials, insofar as they are at all of interest for optical brightening, may be mentioned, but this enumeration is not intended to have any restrictive effect whatsoever.

(I) Synthetic organic high-molecular or higher-molecular materials:

(a) Polymers based on organic compounds containing at least one polymerizable carbon-to-carbon double bond, i.e. their homopolymers and copolymers and the products obtained by after-treating them such, for example, as the products formed by cross-linking, graft polymerization, degradation, polymer blends etc., for example: polymers based on u,B-unsaturated carboxylic acids, especially of acryl compounds (e.g. acrylic esters, acrylic acids, acrylonitrile, acrylamides and their derivatives, or their corresponding methacryl analogs), of olefine hydrocarbons (e.g. ethylene, propylene, isobutylene, styrenes, dienes, especially butadiene, isoprene i.e. also rubber and rubberlike polymers; furthermore, so-called ABS polymers); polymers based on vinyl and vinylidene compounds (such e.g. as vinylesters, vinylchloride, vinylsulfonic acid, vinylethers, vinyl alcohol, vinylidenechloride, vinylcarbazole), of halogenated hydrocarbons (chloroprene, highly halogenated ethylenes), of unsaturated aldehydes and ketones (e.g. acrolein and the like), of allyl compounds and the like, graft polymers (e.g. by graft polymerization of vinylmonomers), cross-linking products (obtained e.-g. with bifunctional or polyfunctional cross-linking agents such as divinylbenzene, polyfunctional allyl compounds or bis-acryl compounds) or products accessible by partial degradation (hydrolysis, depolymerization) or modification of reactive groupings (e.g. esterification, etherifica- :ion, halogenation self-Crosslinking).

(b) Other polymers, such as those accessible by opening of the ring e.g. polyamides of the polycaprolactam type, furthermore formaldehyde polymers, or polymers accessible both by polyaddition and by polycondensation, such as polyethers, polythioethers, polyacetals, thioplasts.

(c) Polycondensates or precondensates based on bifunctional or polyfunctional compounds containing con densable groups, their homocondensates and co-condensates and products obtained by after-treating them, of which the following may be mentioned as examples: Polyesters, saturated (e.g. polyethylene terephthalates) or unsaturated (e.g. maleic acid-dialcohol polycondensates and their cross-linking products with copolymerizable vinylmonomers), unbranched and branched (also on the basis of polyhydric alcohols such, for example, as alkyd resins). Polyamides (e.g. hexamethylenediamine adipate), maleiuate resins, melamine resins, phenolic resins (Novolak), aniline resins, furan resins, carbamide resins and their precondensates and similarly constituted products, polycarbonates, silicone resins and others.

(d) Polyaddition products such as polyurethanes (both cross-linked and not cross-linked), epoxy resins.

(II) semisynthetic organic materials such, for example, as cellulose esters and mixed esters (acetate, propionate), nitrocellulose, cellulose ethers, regenerated cellulose (viscose rayon, cuprammonium cellulose) or their aftertreatment products, casein-based synthetics.

(III) Natural organic materials of animal or vegetable origin, for example based on cellulose or proteins such as wool, cotton, silk, =bast, jute, hemp, skins and hairs, leather, finely dispersed wood masses, natural resins (such as colophony, especially lacquer resins), also rubber, gutta percha, balata and their atfer-treatment and modification products (curing and cross-linking), degradation products (hydrolysis, depolymerization), graft polymerization products, products obtained by conversion of reactive groups (acylation, halogenation, cross-linking or the like).

The organic materials that come into consideration may be in a wide range of processing stages (raw materials, semifinished products or finished products) and physical states. They may be in the form of materials shaped in a Wide variety of Ways, that is to say e.g. predominantly three dimensional objects like blocks, sheets, sections, tubes, injection mouldings or objects machined in a variety of Ways, chips or granules, foamed articles; predominantly two-dimensional materials such as films, foils, lacquers, tapes, coatings, impregnations and coatings or predominantly mono-dimensional materials such as filaments, fibers, fiber tufts, bristles or wires. The afore-mentioned materials may also be in the unshaped state in a Wide variety of homogeneous or inhomogeneous distribution and physical states, e.g. in the form of powders, solutions, emulsions, dispersions, latices (examples: lacquer solutions, polymer dispersions), sols, gels, putties, pastes, waxes, adhesives, pore fillers and the like.

Fibrous materials may take e.g. the form of continuous filaments, staple fibers, fiber tufts, hanks, textile threads, yarns, double yarns, fiber fleeces, felts, cottonwool, flocked materials or of woven textile fabrics or composite textile materials, woven fabrics or of papers and cardboards or paper pulps or the like.

The compounds to be used according to this invention are of special value for the treatment of textile organic materials, especially woven textile wabrics. If fibers are to be optically brightened according to this invention, and are present in the form of staple fibers or continuous fibers, hanks, woven or knitted fabrics, fleeces, flocked substrates or composite materials, this is advantageously carried out in an aqueous medium in which the compound concerned is finely dispersed (suspension, or if desired solution).

If desired, the treatment may be carried out in the presence of a dispersant, e.g. soaps, polyglycol ethers of fatty alcohols, fatty amines or alkylphenols, cellulose sulfite waste liquor or condensates of unmodified or alkylated naphthalenesulfonic acids with formaldehyde. It has proved particularly advantageous to perform the treatment in a neutral, weakly alkaline or acidic bath. It is likewise advantageous to carry out the treatment at a raised tem perature of about 50 to 100 C., for example at the boiling temperature of the bath or in its neighbourhood (at about C.) The improvement according to this invention may also be performed with solutions in organic solvents.

The new optical brighteners to be used in the present process may also be added to or incorporated with the materials before or during the shaping of the latter. Thus, for example, they may be added during the manufacture of films, foils, tapes or shaped materials to the moulding composition or injection moulding composition, or dissolved, dispersed or in any other suitable manner finely distributed in the spinning mass before spinning. The optical brighteners may also be added to the starting materi als, reaction mixtures or intermediate products used for the manufacture of fully synthetic or semisynthetic organic materials, thus also before or during the chemical reaction, e.g. a polycondensation (including the precondensates), a polymerization (including the prepolymers) or a polyaddition.

The new optical brighteners may, of course, also be used wherever organic materials of the kind defined above are combined with inorganic materials in any desired form (typical examples are detergents, white pigments in organic substances).

The new optical brighteners are distinguished by their particularly good thermal stability and fastness to light and migration.

The amount of the new optical brighteners to be used in the present invention, referred to the material to be optically brightened, may vary Within wide limits. Even a very small amount, in some cases e.g. as little as 0.001% by weight, will produce a distinct and durable effect, though amounts of up to about 0.5% by weight or even more may likewise be used. For most practical purposes a preferred amount ranges from 0.01 to 0.2% by Weight.

The new compounds may be used as brightening agents, for example, also in the following manner:

(a) In admixture with dyestuffs or pigments or as additives to dyebaths, printing, discharge and reserve paste. Also for after-treating dyeings, prints or discharge prints.

(b) In admixture with so-called carriers, antioxidants, light filters, heat stabilizers, chemical bleaches or as additives to bleaching baths. 4

(c) In admixture with cross-linking agents or dressing agents such as starches or synthetic dressing agents.

The products of this invention may also be added with advantages to the liquors used for rendering textile materials crease-resistant.

(d) In combination with detergents. The detergents and brightening agents may be added separately to the washing liquors. It is also advantageous to use detergents that as such contain a share of brightener. Suitable detergents are ejg. soaps, salts of sulfonate washing agents e.g-. of sulfonated benzimidazoles substituted by higher alkyl radicals on the Z-carbon atoms; also salts of monocarboxylic acid esters of 4-sulfophthalic acid with higher fatty alcohols; also salts of fatty alcohol sulfonates, alkylarylsulfonic acids or condensation products of higher fatty acids with aliphatic hydroxysulfonic or aminosulfonic acids. Furthermore, there may be used non-ionic washing agents e.g.. polyglycol ethers derived from ethylene oxide and higher fatty alcohols, alkylphenols or fatty amines.

(e) In combination with polymeric vehicles (polymers, polycondensates or polyadducts) in which the brightening agent, if desired together with other substances, may be incorporated in the dissolved or dispersed form, e.g. in the case of coating, impregnating or and the residue is pasted with Water, suctioned, washed binding agents (solutions, dispersions, emulsions) for with water until it is neutral and dried, to yield about textile materials, fleeces, paper or leather. 10.4 g. (=88.8% of theory) of 4,4-di-["-phenyl-1",3",

(f) As additives to a wide variety of industrial prod- 4"-oxdiazolyl-(2")]-stilbene of the Formula 21 O\ O\ fi t-@- @t rQ I l-N N 1l nets to make them easier to market or to obviate shortin the form of a yellow powder melting at 312.5 to comings in their usefulness, for example as additives to 313 C. After three recrystallizations from ortho-dichloglues, adhesives, paints and the like. robenzene with the aid of bleaching earth, pale greenish The compounds of the above formula may also be yellow, very fine needles melting at 319 C. are obtained.

used as scintillators for various photographic purposes An.alysis.C H O N mol weight, 468.49. Calculated such as electrophotographic reproduction or for super- (percent): C, 76.91; H, 4.30; N, 11.96. Found (percent):

sensitizing. C, 76.86; H, 4.16; N, 12.04.

If the brightening process is combined with other treat- The bis-diacylhydrazine of the Formula 20 used as ment or improvement operations this combined treatment starting material can be prepared as follows:

is advantageously carried out with the use of suitable 20 14.0 grams of benzoic acid monohydrazide are stirred stable preparations. Such preparations contain optical in 300 ml. of pyridine, and at 5 to 10 C., 14.5 g. of stilbrighteners of the general formula shown above as well bene-4,4'-dicarboxylic acid dichloride are added. The as dispersants, washing agents, carriers, dyestuffs, pigbatch is stirred for one hour first While cooling with ice, ments or dressing agents. then further at room temperature, and the colorless rather For treating fibrous substrates (especially polyesters) 5 thickly liquid reaction product is heated within a further with the optical brighteners of this invention it is of adhour to 90 to 95 C. After stirring for 5 to 6 hours at 90 vantage to impregnate these fibers with an aqueous disto 95 C. the reaction mixture is cooled to room tempersion of the brightening agents at a temperature below perature and poured into 5 liters of water. The reaction 75 C., e.g. at room temperature, then to subject them to product is suctioned 01f, washed with cold and then with a dry heat treatment at a temperature above 100 C., as a hot water and dried, to yield about 22.6 g. (=80.7% of rule after having advantageously pre-dried it at a modertheory) of bis-diacylhydrazine of the Formula 20 in the ately raised temperature, e.g. at least at 60 C. to about form of a colorless powder which melts at 345 to 100 C. The heat treatment in the dry state is then ad- 345.5 C. vantageously performed at a temperature from 120 to In a similar manner the following dioxdiazole derivato 225 C., for example by heating in a drying chamber, tives can be manufactured:

by ironing within the indicated temperature range or by Yield: 81% of theory. Light yellow, fine crystals from treatment with dry, superheated steam. The drying and ortho-dichlorobenzene, melting at 287 to 288 C.

the dry heat treatment may be carried out immediately Analysis.C H O N mol. weight, 528.54. Calcuone after the other or they may be combined in a single lated (percent): C, 72.71; H, 4.58; N, 10.60. Found (peroperational step. cent): C, 72.24; H, 4.49; N, 10.37.

Example 1 Yield: 87.9% of theory. Greenish yellow, shiny needles and spangles from trichlorobenzene, melting at 379 to 12.6 grams of the bis-diacylhydrazine of the formula 380 C.

NNH NN Analysis.C H O N Cl mol. weight, 537.41.- Calcuin 150 ml. of thionylchloride are stirred under reflux for lated (percent): C, 67.05; H, 3.38; N, 10.43. Found (per- 24 hours. The excess thionylchloride is then distilled off, cent): C, 67.03. H, 3.24; N, 10.40.

Yield: 67.6% of theory. Faintly greenish yellow, very Yield: 78.4% of theory. Light-yellow, very fine crystals line crystals from ortho-dichlorobenzene, melting at from dimethylforrnamide, melting. at 368 to 369 C. 349-350" C. Analysis.-C H O N mol. weight, 470.47. Calcu- AnaZysis.--C H O N mol. weight, 580.70. Calculated (percent): C, 71.48; H, 3.86; N, 17.86. Found (perlated (percent): C, 78.59; H, 6.25; N, 9.65. Found (percent): C, 71.42; H, 4.12; N, 17.89. cent): c, 78.41; H, 6.33; N, 9.84.

Example 2 A mixture of: 38.1 g. of the bis-diacylhydrazine of the formula 5 (31) Yield: 77.4% of theory. Faintly yellowish, shiny, very 2)00\ /C CH fine crystals from ortho-dichlorobenzene, melting at 352-353" C. 0 O

Analysis.C H O N mol. weight, 620.68. Calculated (percent): C, 81.27; H, 4.55; N, 9.03. Found (per- HN-NH cent): C, 81.10; H, 4.63; N, 9.15.

Yield: 82.6% of theory. Yellow, fine, shiny crystals from ortho-dichlorobenzene, melting at 296 to 297 C. 45 and 300 ml. of thionyl chloride is refluxed and stirred Analysis.C I-I O N S mol Weight, 480.57. Calcufor 24 hours. The excess thionylchloride is then distilled lated (percent): C, 64.98, H, 3.36; N, 11.66. Found 011 and the residue triturated with Water, suctioned, washed (percent): C, 64.48; H, 3.34; N, 11.63. with water and dried, to yield about 14.9 g. correspond- O V 0 Q Q -Q Q Q Q ing to 41% of theory, of 4,4'-di[5-para-octoxyphenyl- 1",3",4"-0xdiazo1yl-(2")l-stilbene of the formula H CCH 0 -0 0-0 Yield: 88.5% of theory. Greenish-light yellow, line felted Q N H needles from dirnethylformamide, melting at 367 to 368 C. O

Analysis.-C H O N mol. Weight, 470.47. Calculated (percent): C, 71.48; H, 3.86; N, 17.86. Found (percent): 1 1 1% C, 71.47; H, 3.98, N, 17.88

in the form of a yellow powder which after several recrystallizations, first from dimethyiformamide and then from dioxane, with the aid of active carbon melts at 287 C. It forms light-yellow, fine crystals.

Analysis.-C H O N mol. weight, 724.91. Calculated (percent): C, 76.21; H, 7.23; N, 7.73 Found (percent): C, 76.49; H, 7.33; N, 7.90.

The bis-diacylhydrazine of the Formula 31 used as starting material can be prepared as described in Example 1 from 14.8 g. of stilbene-4,4-dicarboxylic acid dihydrazide (by reacting an excess of hydrazine hydrate upon stiibene-4,4'-dicanboxylic acid diethyl ester at an elevated temperature) and 28.4 g. of para-n-octyloXy-benzoylchloride by reaction in pyridine in a very good yield.

The following dioxdiazole derivatives can be prepared in a similar manner:

which forms colorless, shiny, small crystals from tetrachloroethylene, melting at 282283 C.

Yield: 46.2% of theory. Light, greenish yellow, very fine, felted needles from ortho-dichlorobenzene, melting at 305 to 306 C.

Analysis.C H O N mol. CalCulated (percent): C, 77.40; H, 4.87; N, 11.28. Found (percent): C, 77.66; H, 5.03; N, 11.31.

Yield: 52.4% of theory. Faintly yellowish, very fine crystals from ortho-dichlorobenzene, melting at 336 to 337 C.

Analysis.C H O N mol. weight, 496.54. Calculated (percent): C, 77.40; H, 4.87; N, 11.28. Found (percent): C, 77.26; H, 5.03; N, 11.41.

Example 3 4.7 grams of the compound of the formula Analysis.C H O N mol. weight, 580.70. Calculated (percent): C, 78.59; H, 6.25; N, 9.65. Found (percent): C, 78.33; H, 6.55; N, 9.56.

Example 4 46.5 grams of 2-[4'-methylphenyl-(1')]-5-phenyl-1,3,4- oxdiazole of the formula are fused together with 0.32 g. of flowers of sulfur, and are fused together with 6.4 g. of flowers of sulfur, and

the melt is stirred for 30 minutes at 290 to 300 C. During the cooling, the melt is dissolved in 50 ml. of ortho-dichlorobenzene, and the settled-out crystalline mass is diluted with 50 ml. of methanol. The batch is cooled, suctioned, washed with methanol and dried, to yield about 2.9 g. (=62% of theory) of 4,4'-di-[5"- phenyl 1",3",4"-oxdiazolyl-(2")] stilbene of the Formula (21) in the form of a brownish yellow, crystalline powder melting at 292 to 295 C. After 5 recrystallizations from ortho-dichlorobenzene with the aid of bleaching earth there are obtained light-yellow, shiny, felted needles melting at 317 to 318 C.

Analysis.C H O N mol. Weight, 468.49. Calculated (percent): C, 76.91; H, 4.30; N, 11.96. Found (percent): C, 76.97; H, 4.35; N, 12.00.

the melt is stirred for 1% hours at 290 C. When the evolution of hydrogen sulfide ceases, the melt is dissolved during the cooling with 400 ml. of tetrachloroethylene and then cooled to room temperature. After suctioning, Washing with tetrachloroethylene and drying, there are obtained about 25.9 g. (=55.4% of theory) of 4,4-di- [5" phenyl-l",3",4-oxdiazolyl (2")]-stilbene of the Formula 21 in the form of a brownish yellow powder which after repeated recrystallization from ortho-dichlorobenzene with the aid of bleaching earth forms small, light, greenish yellow, shiny crystals melting at 315 to 316 C.

Analysis.C H O N mol. weight, 468.49. Calculated (percent): C, 76.91; H, 4.30; N, 11.96. Found (percent): C, 77.07; H, 4.56; N, 11.78.

1 5 Example 5 A mixture of 7.4 g. of stilbene-4,4'-dicarboxylic acid iihydrazide, 8.75 g. of 3-chlorobenz0ylchloride, 8 g. of

In a similar manner the following dioxdiazole derivatives can be prepared:

pyridine and 200 ml. of anhydrous ortho-dichloro'benzene ls heated within minutes to to C. while being ;tirred, then further stirred at this temperature for one aour and then heated in the course of 15 to 30 minutes :0 to C. 8 g. of thionylchloride are vigorously methanol and drying there are obtained about 11.7 g. (=87.1% of theory) of 4,4-di-[5"-metachloropheny1- l",3,4"-oxdiazolyl-(2")]-stilbene of the formula Yield: 77.8% of theory. Light-yellow, fine, felted needles from ortho-dichlorobenzene, melting at 299 to 300 C.

Analysis.-C H O N mol. weight, 524.60. Calcu- 15 lated (percent): C, 77.84; H, 5.38; N, 10.68. Found (percent): C, 77.69; H, 5.38; N, 10.58.

OCH;

Yield: 78.5% of theory. Light yellow, finely crystalline powder from ortho-dichlorobenzene, melting at 281 to Analysis.C I-I O N mol. weight, 556.60. Calculated (percent): C, 73.36; H, 5.07; N, 10.07. Found (percent): C, 72.82; H, 5.01; N, 10.11.

OGHa

Yield: 83% of theory. Pale yellow, fine, shiny crystals from ortho-dichlorobenzene, melting at 343 to 344 C.

Analysis.--C H O N Cl mol. weight, 597.46. Calcu- 01 c1 0 o l 1 l l i in the form of a faintly greenish yellow powder melting at 334 to 335 C. Three recrystallizations from ortholated (percent): C, 64.33; H, 3.71; N, 9.38. Found (percent): 0, 64.05; H, 3.50; N, 9.09.

dichlorobenzene with the aid of bleaching earth furnish 65 Yield: 81.6% of theory. Faintly yellow, fine crystals from faintly green, fine crystals melting at 338 to 339 C.

Analysis.C H O N Cl mol. weight, 537.41. Calculated (percent): C, 67.05; H, 3.38; N, 10.43. Found (percent): C, 66.90; H, 3.28; N, 10.22.

ortho-dichlorobenzene, melting at 315 to 316 C.

Analysis.C N O N mol. weight, 520.56. Calculated (percent): C, 78.44; H, 4.65; N, 10.76. Found (percent): C, 78.09; H, 4.81; N, 10.59.

g N-l l N N O 3,511,834 17 18 Yield: 43.3% of theory. Pale yellow, finely crystalline powder from trichlorobenzene, melting at 358 to 360 C. Example 6 AnaZysis.--C H O N mol. weight, 584.56. Calcu- A mixture of 30.5 g. of stilbene-4,4-dicarboxylic acid lated (percent): 0, 69.85; H, 4.14; N, 9.59. Found (perich id 0. g. of para-methylbenzoic acid hydrazide. cent): C, 69.79; H, 4.13; N, 9.52. 32. g. of pyridine and 600 ml. of anhydrous orthodi- B30 /CH3 E00 0 0 OCH ll 1! 1] ll 0 N-N NN 0 Yield: 71.8% of theory. Pale greenish yellow, finely chlorobenzene is heated in the course of 15 to mincrystalline powder from ortho-dichlorobenzene, melting utes to to C. while being stirred, then stirred above 400 C. on at this temperaturei for one hour and in the course Analysis.C H O N mol. weight, 640.67. Calcuof another 20 to 30 minutes heated to 170 C. While lated (percent): C, 71.24; H, 5.03; N, 8.75. Found (pervigorously stirring the almost colorless suspension, 32 g.

cent): C, 71.04; H, 4.95; N, 8.75. 20 of thionylchloride are dropped in at to C.

Yield: 88.5% of theory. Pale yellow, finely crystalline within 20 minutes. The yellow, almost completely dispowder from ortho-dichlorobenzene, melting at 342 to 30 solved reaction product is stirred on at this temperature 343 C. for 5 minutes, cooled to about 5 C. and during the cool- Analysis.C l-I ,O N S mol. weight, 596.64. Calcuing 600 ml. of methanol are added. After suctioning, lated (percent): C, 60.39; H, 3.38; N, 9.39. Found (perwashing with methanol and drying there are obtained t); C, 60 03; H, 3,49; N, 9,33, about 41.8 g. (=84.3% of theory) of 4,4'-di-[5"-meta- 51 i I 0 g 0 M lated (percent): C, 80.26; H, 4.25; N, 9.85. Found (percent): C, 80.18; H, 4.29; N, 9.91.

in the form of a light-yellow powder melting at 267 10 (56) "if t- 15 Yield: 92.2% of theory. Light yellow, very fine, shiny needles from trichlorobenzene, melting at 362 to 364 C.

Analysis.-C H O N mol. 5 weight, 672.75. Calculated (percent): C, 82.12; H, 4.79; N, 8.33. Found (percent): C, 81.40; H, 5.07; N, 8.31.

In a similar manner the following dioxdiazole derivatives can be prepared:

Yield: 70.4% of. theory. Yellow, shiny, small needles from ortho-dichlorobenzene, melting at 273 to 274 C.

Analysis.-C H O N mol. weight, 528.54. Calcu- Yield: 83% of theory. Light yellow, very fine crystals from ortho-dichlorobenzene, melting at 322 C.

OCH;

Analysis.C H O N mol. Weight, 470.47. Calculated (percent): C, 71.48; H, 3.86; N, 17.86. Found (percent): C, 71.75; H, 3.99; N, 17.90.

lated (percent): C, 72.71; H, 4.58; N, 10.60. Found, (percent): C, 72.26; H, 4.46; N, 10.36.

Yield: 67.3% of theory. Yellow, finely crystalline powder from ortho-dichlorobenzene, melting at 326 to 328 C.

ll ll I! ll --N N- Y Analysis.C H O N mol. weight, 588.60. Calcu- 60 lated, (percent): C, 69.37; H, 4.80; N, 9.52. Found (percent): C, 69.06; H, 4.72; N, 9.55.

Yield: 83.2% of theory. Light, greenish yellow, felted crystals from ortho-dichlorobenzene, melting at 337 to 338 C.

Yield: 63.4% of theory. Yellow, finely crystalline powder from ortho-dichlorobenzenc, melting at 275 to 279 C.

Analysis.C gH O N mol. weight, 448.42. Calculated (percent): C, 69.64; H,- 3.60; N, 12.50. Found (per-= HC-CH a Example v7 A mixture of 4.39 g. of the hydrazide of the formula 3.16 g. of 4'-carbethoxystilbene-4-carboxylic acid chloride of the formula 2.4 g. of pyridine and 75 ml. of anhydrous ortho-dichlorobenzene is heated in the course of 15 minutes to 100 to 110 C. while being stirred, then stirred on for one hour at this temperature and then heated to 170 C. Within 15 to 30 minutes. While vigorously stirring the faintly yellow suspension of the reaction product, 3.0 g. of thionylchloride are dropped in at 165 to 170 C. within 15 minutes. The batch is stirred on for minutes at this temperature, cooled to about 5 C. and during the cool ing 100 ml. of methanol are added. After suctioning, washing with methanol and drying there are obtained about 6.2 g. (=88.8% of theory) of 4-[5"-para-tertiary butylphenyl-1,3",4"-oxidiazolyl-(2")] 4'-[5'-(4""-canboethoxy-stilbenyl (4"")) 1"',3',4"' oxdiazolyl-(2"]- stilbene of the formula which after having been recrystallized three times from much orthodichlorobenzene is obtained in the form of a faintly yellow, finely crystalline powder melting at 351 to 352 C.

Analysis.C H O N mol. weight, 698.79. Calcu- HsCzO lated (percent): C, 77.34; H, 5.48; N, 8.02. Found (percent): C, 77.38; H, 5.52; N, 7.95.

The stilbene derivatives of the Formulae 60 and 61 used as starting material can be prepared thus:

A solution of 324 g. of stilbene-4,4-dicarboxylic acid diethyl ester in 1 liter of ethanol and 4 liters of dioxane is mixed at 40 C. With 100 ml. of N-sodium hydroxide solution. After stirring for 1 hour at 40 C. the resulting thick, cream colored paste is cooled to about C., suctioned, washed with dioxane and thoroughly expressed. The moist filter cake is stirred for 2 hours in 10 liters of 5% hydrochloric acid, suctioned and Washed neutral with water. The crude suction filter cake is stirred for 60 minutes in 2 liters of N-aqueous triethanolamine solution and the undissolved material is filtered 0115. The filtrate is 0 CH=OH C\ as a colorless powder whose melting point (230 to 300 C.) depends largely on the speed of heating.

Analysis.C H 0 mol. weight, 296.31. Calculated (percent): C, 72.96; H, 5.44; O, 21.60. Found (percent): C, 72.75; H, 5.40; O, 21.3.

When the acid just described is boiled for 3 hours in an excess of thionylchloride, it gives a yield of 97% of the theoretical of 4-carbethoxy-stilbene-4-carboxylic acid chloride of the Formula 61, in the form of colorless crystals (from trichloroethylene) melting at 134 to 136 C.

Analysis.-C 'H O Cl, mol. Weight, 314.77. Calculated (percent): C, 68.68; H, 4.80; Cl, 11.26. Found (percent): C, 68.28; H, 4.83; Cl, 11.54.

A mixture of 31 g. of 4'-carbethoxy-stilbene-4-carboxylic acid chloride of the Formula 61, 19.3 g. of paratertiary butylbenzoic acid hydrazide and 16 g. of pyridine in 500 ml. of anhydrous ortho-dich orobenzene is heated within 40 minutes to to C. while being stirred, stirred on for 1% hours at this temperature and then raised within 30 minutes to C. While vigorously stirring the almost colorless suspension, 24 g. of thionylchloride are dropped in at 165 C. within 15 minutes.

The yellow reaction product is stirred on for 5 minutes at this temperature, then cooled to about 15 C.; 500 ml. of methanol are added and the precipitated 2-[4- carbethoxy-stilbenyl-(4')] 5 [4"'-tertiary butylphenyl- (1"') ]-1,3,4-oxdiazole of the formula is suctioned off, washed with methanol and dried, to yield about 25.1 g. (=55.5% of theory) of a faintly yellow, finely crystalline powder melting at 198 to 199.5 C. After having been recrystallized three times from tetrachloroethylene with the aid of bleaching earth it forms pale yellow, very fine needles melting at 200.5 to 201.5 C.

Analysis.C H O N mol. weight, 452.53. Calculated (percent): C, 76.97; H, 6.24; N, 6.19. Found (percent): C, 76.67; H, 6.20; N, 6.10.

By boiling the ester of the Formula 64 in methylglycol for 48 hours under a slight reflux with an excess of hydrazine hydrate it is converted into the hydrazide of the Formula 60 which melts at 262 C. with decomposition.

In a similar manner the following dioxdiazole derivaacidified with concentrated hydrochloric acid, and the 75 tives can be prepared:

Yield: 88.9% of theory. Light yellow, finely crystalline powder from ortho-dichlorobenzene, melting at 361 to 362 C.

Analysis.C H O N mol. weight, 641.73. Calculated (percent): C, 76.74; H, 4.87; N, 10.91. Found (percent): C, 76.42; H, 4.78; N, 10.79.

Yield: 85% of theory. Yellow, fine crystals from trichlorobenzene, melting at 379 to 380 C.

Analysis.-C H O N S, mol. weight, 647.76. Calculated (percent): C, 72.32; H, 4.51; N, 10.81. Found (percent): C, 71.94; H, 4.48; N, 10.79.

Example 8 3.9 g. of the compound of the formula dine are added. The batch is then heated for 2 hours at 75-80 C. and for one hour at 100-105 C. 2.6 ml. of thionyl chloride are then added dropwise at 160-170 C. in the course of one hour, the batch is stirred for 25 minutes at 160 C., cooled to room temperature, the crystalline product is filtered with suction and recrystallized twice from 500 ml. of trichlorobenzene with the aid of fullers earth.

are suspended in 100 ml. of ethyleneglycolmonomethyl Yield: about 3.1 g. of the compound l t l. l

ether with stirring. The mixture is heated to the boil, 1.8 ml. of sodium hydroxide solution of 30% strength are added dropwise in the couse of one hour and the batch is then boiled under reflux for 16 hours. After cooling, the reaction mixture is filtered with suction, the product washed with methanol, boiled with 300 ml. of trichlorobenzene, filtered while hot, the residue washed with methanol and recrystallized twice from a mixture of 300 ml. of water and 300 ml. of pyridine with the addition of about 7 g. of sodium chloride.

Yield: about 1.6 g. (47.6% of the theory) of the compound Pale yellow needles. Melting point: 335335.5.

Analysis.-C H N S O Calculated (percent): C, 64.61; H, 3.61; S, 8.21. Found (percent): C, 64.60; H, 3.68; S, 8.30.

The phenyl ester of 4-sulfobenzoyl chloride of Formula 69 used as starting material may be prepared as follows: 110 g. (0.5 mol) of 4-car-hoxybenzene sulfochloride are introduced with cooling on an ice-bath into a solution of 188 g. (2 mols) of phenol in 500 ml. of dry pyridine in such a way that the temperature does not rise above 5 C. The batch is stirred for 30 minutes at 05 C., the temperature of the resulting, pale brown, clear solution is allowed to rise to room temperature, the batch is then heated within an hour to 100 C., cooled again, poured dropwise with stirring on to 2.5 kg. of ice, acidified at 0-5 C. dropwise with 450 ml. of concentrated hydrochloric acid, the white precipitate filtered with suction and washed neutral with ice-water. After drying under reduced pressure, initially at 40 C., and then at C.,

there are obtained 74.5- g. of a grey sticky mass which by: recrystallization from double the quantity of chlorobem zene yields 21.1 g. of colorless crystals melting at 208- corresponding dodecylamide is obtained. In a similar 210 C. manner also the anilide, the benzylamide and the mor- A further recrystallization yields the compound of the pholide may be prepared. immula Example 10 71) o o A bleached cotton fabric is washed at 60 c. for 30 minutes at a goods-to-liquor ratio of 1:30 in a liquor conin the form of colorless crystals melting at 211-212 C. taining, per liter.

Analysis.C H O S (278.28). Calculated (percent): 0.024 g. of the brightener of the formula C, 56.11; H, 3.62; S, 11.52. Found (percent): C, 56.18; 1 g. of active chlorine (javelle water) H, 3.58; S, 11.63. 4 g. of a detergent of the following composition: Percent By reaction with 14.5 ml. of thionyl chloride in 100 ml. Dodecylbenzene sulfonate 15.00 of chloroform in the presence of 0.3 ml. of pyridine for Sodium-lauryl sulfonate 10.00 one hour at reflux temperature and subsequent evapora- Sodium tripolyphosphate 40.00 tion there are obtained 24.5 g. of crude acid chloride of Calcined Glaubers salt 25.75 the formula Sodium metasilicate 7.00 Carboxymethyl-cellulose 2.00 (69) Ethylenediamine-tetraacetic acid 0.25 o soz cocl After being rinsed and dried, the fabric shows a very considerable brightening effect of good fastness to light, in the form of a colorless oil that on cooling crystallizes acld and chlormealmost throughout and melts at 9798 C. Recrystalliza- Example 11 tion from methylene chloride yields colorless crystals of A 60 C, a fabri d f l id fib (Perunchanged melting Point y are, however, y Sensilon) is entered at a goods-to-liquor ratio of 1:40 into a tive to hydrolysis and for further processing must be bath containing (referred to the weight of the fabric) treated afresh with thionyl chloride. 0.2% of the brightener of the formula j 0 NaO S-fi fi -cH=cH- o c--soma N Il ll Example 9 and, per liter, 1 g. of 80% acetic acid and 0.25 g. of an The compound according to Formula 68 can be transadduct of 30 to 35 mols of ethylene oxide and 1 mol formed into the corresponding disulfonic acid dichloride of commercial stearyl alcohol. In the course of 30 minof the formula utes, the bath is heated to the boiling temperature and NN NI I in usual manner. l so maintained for 30 minutes. After rinsing and drying, 33.2 g. of the crude disulfonlc acid dichloride of the a very considerable brightening eifect of very good light Formula 72 in mixture with 350 ml. of n-octylamine are fa tne s i obt i d heated at 75-80 C. for 3 hours. After cooling to room E 1 12 temperature, the crystalline product is filtered off with Xamp e suction, washed with methanol and recrystallized twice A bleached woven fabric from polyamide staple fiber from dimethylformamide with the use of fullers earth. (nylon spun) is treated at a goods-to-liquor ratio of Yield, about 23.2 g. (54.6% of the theoretical) of the 1:40 for 60 minutes at 60 C. to 100 C. in a bath concompound taming-referred to the fibrous material-0.025% of the CH /0\ /0\ CH3 QB: t@- CN NN fine, pale yellow crystals, melting point 300. compound of the Formula 28 and 2 g. per liter of a dis- Analysis.C H N O S Calculated (percent): C, persant (adduct from 35 mols of ethylene oxide and 1 64.92; H, 6.40; N, 9.87. Found (percent): C, 64.79; H, mol of octadecyl alcohol). After having been rinsed and 6.48; N, 9.77. dried, the fabric treated in this manner displays an out- By using dodecylamine instead of n-octylarnine the 75 standing brightening effect.

When the polyamide staple fiber fabric is replaced by a polyamide filament fabric, similar good brightening effects are obtained.

Example 13 Example 14 Q kilograms of a polyamide inchip form, manufactured from hexamethylenediamine adipate in the known manner, are mixed with 30 g. of titanium dioxide (rutile modification) and 5 g. of a compound of one of the For mulae 22, 25, 33, 34, 36 or 52 in a tumbler for 12 hours. The chips treated in this manner are then melted in a boiler from which the atmospheric oxygen has been displaced with superheated steam and which is heated by oil or diphenyl vapour at 300 to 310 C., and the melt is stirred for /2 hour, then expressed through a spinneret under a nitrogen pressure of 5 atmospheres (gauge), and the filament spun in this way is reeled on a spinning bobbin after cooling. The resulting filament displays an excellent brightening effect which is stable towards heatsetting and has good fastness to washing and light.

When the starting material used in the above example I is a polyamide manufactured from e-caprolactam, an excellent brightening eifect which is stable to heat-setting and has good fastness to washing and light is likewise obtained.

Example 15 100 g, of polyester granulate from polyterephthalic acid ethyleneglycol ester are intimately mixed with 0.04 g. of the compound of the Formula 22 or 52 and fused at 285 C. while being stirred. When the spinning mass is spun through a conventional spinneret, considerably brightened polyester fibers are obtained.

28 Example 17 An intimate mixture of g. of polyvinylchloride, 3 g. of stabilizer (Advastol ED 100; barium-cadmium complex), 2. g. of titaninum dioxide, 59 ml. of dioctylphthalate and 0.02 to 0.1 g. of the compound of the Formula 25 is rolled on a calender heated at 150 to 155 C. to form a foil. The polyvinylchloride foil obtained in this manner has a significantly higher white content than a foil that does not contain the dioxdiazole compound.

A good optical brightening efiect is also obtained when polyvinylchloride is replaced by polyethylene and the treatment is performed at a temperature of to C.

We claim:

1. The 4,4'-disubstituted stilbene compound of the formula 1% ---N NN wherein A and A represents a member selected from the group consisting of the phenyl, naphthyl, styryl, stilbenyl, pyridyl, thienyl, furoyl, benzoxazolyl thienyl and benzoxazolyl phenyl residue which itself contains one to two substituents Q, in which Q standsfor a member selected from the group consisting of hydrogen, chlorine, bromine, alkyl containing 1 to 18 carbon atoms, alkoxy containing 1 to 8 carbon atoms, phenyl, carboxyl, carboxylic acid alkyl ester of 1-18 carbon atoms, carboxylic acid phenylalkylester with 1-4 carbon atoms in the alkyl, carboxylic acid amide, nitrile, carboxylic acid alkyl amide with 1 to 12 carbon atoms, carboxylic acid morpholide, carboxylic acid anilide, carboxylic acid phenylalkyl amide with 1-4 carbon atoms in the alkyl, sulfonic acid, sultonic acid alkyl ester containing 1-18 carbon atoms, sulfonic acid benzylester, sulfonic acid phenyl ester and sulfonic acid amide, sulfonic acid alkyl amide containing 1 to 18 carbon atoms, sulfonic acid benzylamide and sulionic acid anilide.

2. The 4,4'-symmetrical disubstituted stilbene compound according to claim 1 which corresponds to the formula I O /O\ t" i i-ii N -1i If desired, the compound of the Formula 22 or 52 may alternatively be added to the starting materials before or during the polycondensation leading to the polyester.

Example 16 100 g. of polypropylene fiber grade are intimately mixed with 0.02 g. of the compound of the Formula 32 and fused at 280 to 290 C. while being stirred. After atoms and sulfonic acid amide.

3. The symmetrical stilbene compound according to claim 1 which corresponds to the formula spinning through conventional spinnerets and stretching, polypropylene fibers are obtained which display an excellent brightening efiiect which is fast to light.

where Q represents an alkyl group containing to 4 carbon atoms.

4. The compound according to claim 1 of the formula wherein Q represents the sulfonic acid group, Water soluble salt of the sulfonic acid, sulfonic acid alkyl amide containing 1 to 12 carbon atoms, sulfonic acid alkyl ester containing 1 to 12 carbon atoms and the sulfonic acid phenyl ester which may be substituted by lower alkyl. 5 5. The compound according to claim 1 of the formula N N l i wherein X stands for hydrogen, alkali metal, ammonium or an amine salt ion.

6. The compound according to claim 1 of the formula 15 H 0 NN CH 7. The compound according to claim 1 of the formula 8. The compound according to claim 1 of the formula II N 9. The compound according to claim 1 of the formula 1 N N i i I 10. The compound according to claim 1 of the formula it 1% l t 11. The 4,4'-disubstituted stilbene compound as acid amide, nitrile, sulfonic acid, lower alkyl sulfonic claimed in claim 1 of the formula 5 acid ester and sulfonic acid amide.

0 0 I References Cited S fi- CH=OH ii UNITED STATES PATENTS --N 3,351,591 11/1967 Siegrist et a1. 260-240 where A represents a member selected frornthe group 60 HENRY LES, Primary Examiner consistlng of a phenyl, naphthyl and styryl residue which itself may contain one to two substituents Q, in which Q TODD, Asslstant aminer stands for a member selected from the group consisting of hydrogen, chlorine, bromine, alkyl containing 1-8 carbon atoms, alkoxy containing l-8 carbon atoms, phenyl, 65 96 1, 104; 106 193; 117 33 5, 102; 162 162; 252 carboxyl, lower alkyl canboxylic acid ester, carboxylic 301.2; 260-37, 41, 240.1, 471, 475, 558, 559

$2233?) UNITED STATES PATENT OFFICE CERTIFICATE 6F CORRECTION Patent No. 3, 5 a 3 Dated y 97 Inventor(3) ADOLF EIKIL SIEGRIST ET AL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 28, claim 3, line 1 after the structural formula,

insert after the word contair.i:1;; the number 1 Signed and sealed this 15th day of June 1971.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JR. Attesting Officer Commissioner of Patents 

